Anthraquinone dyes



United States Patent 3,538,127 ANTHRAQUIN ONE DYES Hans Rudolf Schwander, Riehen, Anton Zenhausern,

Reinach, Basel-Land, and Peter Hindermann, Bottmingen, Basel-Land, Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Continuation-impart of application Ser. No. 645,514, June 12, 1967, now Patent No. 3,499,915, which is a continuation-in-part of application Ser. No. 514,692, Dec. 17, 1965, now Patent No. 3,431,285. This application Mar. 28, 1968, Ser. No. 716,978

Int. Cl. C091) 1/40 U.S. Cl. 260-372 6 Claims ABSTRACT OF THE DISCLOSURE 1,4-diamino-anthraquinone dyes which are substituted at the amino nitrogen in l-position by a secondary alkyl or by a cycloalkyl group, and which are substituted at the amino nitrogen in 4-position by a diaralkyl substituent the aryl moiety of which is substituted by AO H and a fiberreactive grouping especially of the CCl=CH or CH Cl type, which fiber-reactive grouping is linked to the said aryl moiety via a CO-NHCH type (Einhorn) bridge; these dyestuffs being useful as substantive, and as far as they possess fiber-reactive groupings, as reactive polyarnide dyes.

RELATED APPLICATIONS This application is a continuation-in-part application of our pending patent application Ser. No. 645,514, filed June 12, 1967, now U.S. Pat. 3,499,915, which is in turn a continuation-in-part of our pending patent application Ser. No. 514,692, filed Dec. 17, 1965, now U.S. Pat. 3,431,285.

DESCRIPTION OF THE INVENTION The present invention concerns new fiber-reactive acid anthraquinone dyestuffs, processes for the production thereof, their use for the dyeing and printing of polyamide fibers as well as, as industrial product, the material dyed and printed therewith.

A great number of anthraquinone dyestuffs having very good fastness properties, particularly wet fastness properties, are known. But some of them are unsatisfactory in certain respects, for example insufficient drawing power from a neutral bath, tendency to produce tippy dyeings, insufiicient brilliancy or they cannot be combined well with other dyestuffs of this class.

Thus, while certain blue anthraquinone dyestuffs described in the aforesaid application Ser. No. 645,514 can be mixed with yellow dyestuffs of other classes which dye polyarnide fibers, especially nylon or wool, from an acid exhaustion bath, in order to obtain various green shades, it is not possible to use these anthraquinone dyes for the dyeing of blended fiber materials containing the aforesaid polyarnide fibers and another non-polyamide fiber component, if the latter component requires dyeing from a substantially neutral dyebath. They are also not suitable for the dyeing of the above mentioned polyarnide fibers or the aforementioned blended fibers when they are to be used in mixture with yellow dyes of other dyestuif classes, for the purpose of obtaining green shades, if these yellow dyes do not permit use of an acid exhaustion bath but draw only from a substantially neutral medium.

These requirements are fully met by dyestuffs accord ing to the present invention. Moreover these new dyestuffs yield dyeings on the above-mentioned polyarnide and blended fiber materials which are distinguished by specially outstanding wet fastness properties and 'brilliancy, espe- Patented Nov. 3, 1970 cially including green shades obtained by mixture with neutral-drawing yellow dyes from other dyestuff classes.

Blended fiber materials contain besides the polyarnide fibers, cellulosic fibers such as cotton, cellulose acetate including cellulose triacetate, polyethyengyco-terephthaate fiber or the like.

The new dyes according to the invention are distinguished apart from fulfilling the requirements explained in the foregoing, by excellent level drawing property on the above-mentioned polyarnide blended fibers, and by satisfactory to very good light fastness of the resulting dyeings on these fibers, even in green shades obtained by using the above-mentioned mixtures of the new dyes with suitable neutral-drawing yellow dyes.

Yellow dyes which draw from a neutral bath on the above-mentioned fibers and are particularly suitable for mixture with the neutral-drawing anthraquinone dyes according to the invention are those of the following classes: benzene-azo-pyrazolone dyes, benZene-azo-imino-pyrazole dyes, pyraZolone-azoarylene-azo-pyrazolone dyes or iminopyrazole-azoarylene-azo-iminopyrazole dyes.

A first class of these new dyestuffs falls under the Formula I and a second class under the Formula II NH-eycloalkyl wherein:

each of R and R represents a lower alkyl group,

R, represents a divalent arylenealkyl group linked with its alkyl moiety to .CljH and with its arylene moiety to the SO H group, and being unsubstituted or ring-substituted by lower alkyl and/ or lower alkoxy groups and/or by halogen,

R' is an alkyl or cycloalkyl radical or an aralkyl radical, the latter being linked by its alkyl moiety to the CH group in said formulas and being unsubstituted or ringsubstituted by lower alkyl and/or lower alkoxy groups and/ or by halogen,

R represents hydrogen or lower alkyl,

cycloalkyl means preferably the unsubstituted cyclopentyl or cyclohexyl group or a lower alkyl-substituted cycopentyl or cyclohexyl group,

A represents an alkenyl group which can optionally contain at least one substituent which can be split off as ion, and which can be substituted, e.g. by lower alkyl and/or halogen, or it represents an alkyl group which contains at least one substituen-t which can be split off as ion and which can be substituted, e.g. by phenyl and/ or halogen,

m represents 1 or 2 and n is a number ranging from 1 More in detail, in preferred subclasses of the dyestuffs falling under Formulas I and II,

R,, represents the same alkyl or cycloalkyl radical as represented by R in Formula V, infra, or when R represents aralkyl, the corresponding monoor polyvalent aralkyl group, the radicals R and R' together having a total of at least three and not more than five free bonds, and the number of aryl moieties in R'.; and R' counted together being preferably not more than two, and preferably one,

R', represents a monoor polyvalent aralkyl radical preferably with one mononuclear carbocyclic, aryl moiety, which corresponds to the radical R in Formula V, infra, and the groupings -SO H and -CH2NC A 1'1,

are each bonded to carbon atoms of the aryl nuclei in the aralkyl moieties R'.; and/ or R' The acid anthraquinone dyestuffs according to the invention are suitable for the dyeing and printing of synthetic polyamide fibers, primarily nylon, e.g. nylon 6 or nylon 66, or polyurethanes, or, secondarily of natural polyamide such as silk, leather and, particularly, wool. They draw onto these fibers from a weakly acid to acid bath at higher temperature evenly and cover barriness of nylon very well. Compounds according to the invention of Formulas I and II which contain two radicals CH N(R )COA are advantageously dyed from a weakly acid bath in the presence of a dyeing auxiliary such as an addition product of about -20 mols of ethylene oxide to a fatty acid alkanolamide. Compounds of Formulas I and II which contain only one radical have particularly high drawing power from a neutral bath.

The blue dyeings obtained, particularly the wool dyeings, are distinguished by high brilliancy as well as by fastness to rubbing, good light fastness and good wet fastness properties, particularly fastness to washing, milling and sea water. In addition, the dyestuffs according to the invention are suitable for use in admixture with other acid dyestuffs to attain combination dyeings.

In some cases the new dyestuffs according to the invention can be used for the dyeing of cellulose material, particularly cotton. Dyeing of this material is performed by the methods usual for reactive dyestuffs.

A preferred subclass of dyestuffs according to the invention comprises the dyestufi of the Formula III:

Q represents one of the radicals cyclopentyl or cyclohexyl, and each of R and R represents lower alkyl,

(III) wherein:

R represents alkylene of from 1 to 2 carbon atoms,

A represents lower alkyl of from 1 to 4 carbon atoms or lower alkenyl of from 2 to 3 carbon atoms, each of which is substituted by from one to two halogen atoms selected from chlorine and bromine,

each of Z and Z represents hydrogen, methyl, methoxy,

cyclopentyl or cyclohexyl,

each of Z and Z represents hydrogen, methyl or methq represents 0 or 1, and

p ranges from 1 to 2 not more than one SO H group being linked to each of the two benzene nuclei.

Another preferred subclass of dyestuffs according to the invention comprises the dyestuff of the Formula IIIa Q represents one of the radicals R1 CH cyclopentyl or cyclohexyl,

each of R and R represents lower alkyl,

R represents alkylene of from 1 to 2 carbon atoms,

each of Z and Z represents hydrogen, methyl, methoxy,

chlorine or bromine,

each of Z and Z represents hydrogen, methyl or methoxy, and

A represents an alkenyl radical of from 2 to 4 carbon atoms, especially the CH=CH or group,

q represents 0 or 1, and

p ranges from 1 to 2, not more than one SO H group being linked to each of the two benzene nuclei.

The drawing power on nylon of the dyestuffs according to the invention, and particularly of those falling under Formulas III and 11101 is particularly superior to that of the corresponding dyestuffs in which ring B is directly linked to the amino group in 4-position at the anthraquinone nucleus. The same applies to fastness of nylon dyeings obtained with the novel dyestuffs to rub bing and to milling.

Dyestuffs falling under Formulas III and BM in which Q represents the grouping and particularly isopropyl, are particularly superior to the correspondingly substituted last-mentioned known dyestuffs in that their dyeings on synthetic polyamide fibers, and especially on texturized nylon (e.g. Banlon) show superior fastness to rubbing, and their dyeings on'staple rayon are particularly superior in fastness to perspiration, especially alkaline perspiration.

The unsulfonated dyestuffs according to the invention and particularly those corresponding to Formulas III and IIIa but being free from sulfonic acid groups, are useful as disperse dyestuffs for the dyeing of polyamide fibers; the dyeings show good wet fastness properties.

Higher sulfonation, e.g. with one and a half, two or wherein Q represents a secondary alkyl or a cycloalkyl group and X represents a substituent which can be exchanged for an aralkylamino group, for example chlorine, bromine, the hydroxyl or a lower alkoxy group, such as the methoxy group, or the nitro or amino group; chlorine or bromine being preferred,

with an aralkylamine containing at least two replaceable hydrogen atoms in the nucleus of the Formula V:

wherein R represents an aralkyl group optionally ring substituted by lower alkyl or lower alkoxy groups or by halogen, and R represents an alkyl group, a cycloalkyl group or an aralkyl group optionally ring-substituted by lower alkyl and/or lower alkoxy groups and/or by halogen, to form the corresponding l-sec. alkylaminoor 1-cycloalkylamino-4-aralkylamino-anthraquinone and, in any order desired, reacting the latter with n mol of a sulfonating agent and with 111 mol of a compound introducing the radical of the Formula VI:

OHz-NC O-A wherein:

R represents hydrogen or a lower alkyl group and A has the same meaning as in formulas I and II,

to form an anthraquinone dyestuff of the average composition as defined in Formula I or II, respectively.

If Q is a secondary alkyl group then this advantageously contains at most 6 carbon atoms and is, e.g. the isopropyl, sec. butyl or see. isoamyl group. When Q is a cycloalkyl group it is preferably a mononuclear group such as the cyclopentyl or cyclohexyl group or homologues thereof, or it is a polynuclear non-condensed cycloalkyl group such as a dodecahydrodiphenyl group or a polynuclear condensed group such as decahydronaphthyl- (1)- or -(2)-group.

Advantageously Q represents the isopropyl, sec. butyl or cyclohexyl group.

Aralkyl groups in the position of R and R are above all a-arylalkyl or B-arylalkyl groups, the aryl ring preferably being mononuclear. Examples thereof are the benzyl or phenethyl group. The aralkyl radicals in the positions of R and R can also contain two benzene nuclei. In this case they are, e.g. radicals of a Bfi-diphenylethane. If the aryl rings of the aralkyl groups are substituted by low alkyl or alkoxy groups then these groups advantageously are, for instance, the methyl or ethyl group and the methoxy or ethoxy group, respectively; if they are substituted by halogen then this is for example fluorine, bromine or especially chlorine. The aliphatic part of the aralkyl radical can be straight or branched chained.

As alkyl group, R is for example the methyl, ethyl or isobutyl group. When R is a cycloalkyl group, it is preferably the cyclohexyl group.

In preferred aralkylamines of Formula V, R; is a phenylalkyl radical, especially the benzyl or phenethyl radical, and R is a low alkyl group, preferably the methyl group.

X in Formula IV represents, e.g. chlorine, bromine, the hydroxyl group, low alkoxy groups such as the methoxy group, or the nitro or amino group. However, X is preferably chlorine or bromine.

If R-; is a low alkyl group then it is advantageously a methyl or ethyl group; more preferably, however, R is hydrogen.

When A is an alkenyl group, it has at most 4, but advantageously 2 or 3 carbon atoms and not more than one double bond and is, e.g. a vinyl, propenyl, isopropenyl, l-methylpropenyl, allyl or methallyl radical. If A is an alkyl group then it preferably contains 1 to 4 carbon atoms.

The substituents which can be split oil as ion may be split oil as anion or cation. Examples of the former are halogens such as chlorine or bromine, an alcoholic hydroxyl group asterified with sulphuric acid or with aliphatic or aromatic sulphonic acid, or the group RO, RS and RSO wherein R is an organic radical such as an aliphatic or aromatic hydrocarbon radical. Examples of groups which can be split off as cation are quaternary ammonium groups such as the trimethyl ammonium group, the group Preferably A contains a halogen atom in the u-position to the -CO group and it is for example the chloromethyl, bromomethyl, a-chlorovinyl or a-bromovinyl group.

There can be one or more groups present in the radical A which can be split off as anion or cation.

When the alkyl groups are further substituted and the alkenyl groups are substituted or further substituted, they contain, e.g. a hydroxyl, carboxyl or aryl group, in the latter case preferably the phenyl group.

Example of A are:

In the above, Hal represents chlorine or bromine, R represents an alkyl group and Ar an aryl group.

In preferred compounds introducing the radical of Formula VI, A is the chloromethyl or the ix-chlorovinyl group and R is hydrogen.

Starting materials of Formula IV are obtained by known processes, e.g. by chlorinating or brominating or nitrating the corresponding l-sec. alkylaminoor l-cycloalkylamino-anthraquinone compounds and, if desired, exchanging the chlorine or bromine for the hydroxyl or a low alkoxy group, or reducing the nitro group to the amino group. Starting compounds of Formula IV wherein X is the hydroxyl group can also be obtained by reacting 1,4-dihydroxyanthraquinone or its leuco compound or a mixture thereof with the corresponding sec. alkylamine or cycloalkylamine. They can be used direct for reaction with the aralkylamine of Formula V without isolation.

The aralkylamines of Formula V are obtained, according to R. Leuckart, Ber. 18, 2341 (1885) for example, by reacting ketones of the formula with ammonium formate or formamide and then splitting off the formyl group. In some cases, they can be obtained according to G. Mignonac Or. 172, 223 (-1921) by converting an arylidene ketone into the saturated amine with ammonia and hydrogen in the presence of a catalyst.

Examples of compounds which can be used to introduce the radical of Formula VI are the N-methylolamides or N-(chloromethyl)- or N-(bromomethyl)-amides of corresponding carboxylic acids of the formula:

Z OH2NO oA it. wherein Z represents the hydroxyl group or chlorine or bromine.

The N-methylolarnides are obtained, e.g. by adding formaldehyde to the corresponding carboxylic acid amides in the presence of basic condensing agents such as potassium carbonate, or also by reaction with mineral acid under mild conditions, and the N-(chloromethyl)- or N- bromomethyl)-amides are obtained by reacting the methylolamides mentioned above with, e.g. thionyl chloride or thionyl bromide. Instead of the N-methylolamides or N-(halogenomethyl)-amides, also other reactive functional derivatives which react in the same Way can be used, e.g. other esters of the methylol compounds with inorganic acids. Also the di-(carboxylic acid amidomethyl)-ethers obtained by condensation of the methylolamides in the presence of, e.g. phosphorus oxychloride, can be used. However, as these functional derivatives often have to be produced from the corresponding methylol compounds, the latter are preferred.

The reaction of the anthraquinone compound of Formula IV with the aralkylamine of Formula V is performed, e.g. in solution or in the melt of an excess of aralkylamine as defined or in an organic solvent not taking part in the reaction. Preferable solvents for this purpose are, e.g. aromatic hydrocarbons such as toluene, xylenes or naphthalene; or hologenated or nitrated aromatic hydrocarbons such as chlorobenzene, diand trichlorobenzene or nitrobenzene; or halogenated aliphatic hydrocarbons such as trichloroethylene; alcohols, e.g. alkanols such as n-butanol, sec. butanol or alkylene glycol monoalkyl ethers e.g. ethylene glycol monomethyl or monoethyl ether; aromatic hydroxyl compounds, e.g.

phenol and its homologues; or tertiary nitrogen bases such as pyridine.

If, as starting material, an anthraquinone compound of Formula IV is used wherein X is halogen, especially chlorine or bromine, the reaction is advantageously performed in the presence of copper or a copper compound such as cuprous chloride and in the presence of an acid bulfering agent and, preferably at a raised temperature.

As acid buffering agent, advantageously an excess of the aralkylamine as defined is used, optionally together with an alkali metal salt of a fatty acid such as sodium or potassium acetate or of carbonic acid, such as sodium bicarbonate or sodium carbonate, or with an alkali metal hydroxide such as sodium or potassium hydroxide, or with magnesium oxide. In some cases, a tertiary amine such as triisopropanol-amine can be used as buffering agent.

The reaction of the l-sec. alkylaminoor l-cycloalkylamino-4-aralkylamino-anthraquinone compound with the compound introducing the radical of Formula VI is performed advantageously in the presence of acid condensing agents or agents splitting off water which react as such condensing agents. Examples of such condensing agents are concentrated hydrochloric acid, zinc chloride, phos phorous pentoxide, acetic acid anhydride, syrupy phosphoric acid and oleum. The preferred condensing agent, however, is to anhydrous sulphuric acid. The reaction temperature can fluctuate within wide limits and depends mainly on the condensing agent used. In concentrated sulphuric acid, the reaction generally proceeds quickly and completely even at room temperature; in some cases a slightly raised temperature is necessary. The finished reaction products are precipitated, for instance, by pouring the sulphuric acid solutions or suspensions into ice water and they are converted into the water soluble alkali metal salts in the usual way and these are isolated.

In some cases, instead of the aforesaid N-methylolamides or N-halogenomethylamides a mixture of a,a-dichloroor a,ot'-dibromo-dimethyl ether with the corresponding carboxylic acid amides or with carboxylic acid nitriles, such as acrylonitrile or a halogen acrylonitrile can be used as compounds introducing the radical of Formula VI. In this case too, the reaction is advantageously performed in concentrated sulphuric acid. (This method of performing the process according to the invention is described, for example, in the following Belgian Pats: 630,205; 625,916; 628,442; 608,932; 613,037; 603,420; 612,417).

The sulphonation is performed by usual methods, for instance, in concentrated sulphuric acid or in oleum under mild conditions, e.g. at room temperature, or which chlorosulphonic acid in a solvent which is inert under the reaction conditions.

In a preferred method, sulfonation is carried out with oleum having an SO -content of at least 3 but not more than about 10% by weight, preferably, however about 6 to 7%, at room temperature (15 to 35 C.) The degree of sulfonation attained is controlled by testing the solubility of samples or other known methods which have been mentioned under the first aspect of the invention.

Isolation and identification of isomers constituting the dyestufis of the invention could be achieved by the methods described under the first aspect of the invention, but they are of no practical value for the same reasons as stated thereunder.

A technically particularly simple and, therefore, preferred method consists in the condensation of the l-sec. alkylaminoor l-cycloalkylamino-4-aralkylaminoanthraquinone compound with the compound introducing the radical of Formula VI or precursors thereof and sulfonation of the condensation product obtained without isolation of the intermediate product. This condensation is performed in concentrated sulfuric acid wherupon the condensation product obtained is sulfonated in sulfuric acid solution.

The two operations last mentioned are advantageously so arranged that not more than one radical of Formula V and one sulfonic acid group are introduced per aralkyl radical having at least two replaceable hydrogen atoms in the nucleus.

A first modification of the process according to this aspect of the invention consists in reacting an anthraquinone compound of Formula VII:

O X (VII) wherein Y represents an acyl radical and Q and X have the meanings given above,

with an aralkylamine, having at least two replaceable hydrogen atoms in the nucleus, of Formula V to form the corresponding l-(N-sec. alkyl-N-acylamino)- or 1-(N- cycloalkyl-N-acylamino)-4 aralkylamino-anthraquinone compound and, in any order desired, saponifying this into the corresponding l-sec. alkylaminoor l-cycloalkylamino- 4 aralkylamino-anthraquinone compound and reacting with n mol of a sulfonating agent and m mol of a compound introducing the radical of Formula VI to form an anthraquinone dyestutf mixture of the average composition of Formula I or II respectively.

Y represents, eg a carbacyl radical, particularly an alkanoyl radical, e.g. the formyl, acetyl or propionyl radical, or an aroyl radical such as the benzoyl radical, or an alkyl-sulfonyl radical such as the methylsulfonyl radical, or an arylsulfonyl radical such as the phenylsulfonyl or pmethylphenyl sulfonyl radical. Preferably Y is the acetyl radical.

The l-acylamino-anthraquinones of Formula VII are obtained by known methods, e.g. by reacting an anthraquinone compound of Formula IV with an acylating agent introducing the-radical Y, mainly with acetyl chloride or bromide or acetoanhydride.

The reaction of the l-acylamino-anthraquinone compound of Formula VII with the aralkylamine of Formula V is performed as described in the first process. Preferably, the l-(N-sec. alkyl-N-acylamino)- or l-(N-cycloalkyl-N- acylamino) 4-aralkylamino-anthraquinone compound is first saponified, then reacted with the compound introducing the radical of Formula VI and finally sulfonated. Saponification is performed advantageously in aqueous acid medium, e.g. in aqueous sulfuric acid and, advantageously, at a raised temperature. The reaction with the compound introducing the radical of Formula VI and the sulfonation are performed as described in the first process of the invention.

The quantitative reaction of an acylamino-anthraquinone compound of Formula VII with an aralkylamine of Formula V and the subsequent quantitative Saponification of the acyl radical are unexpected, as normally when arylamines are used instead of aralkylamines, insufficient yields are obtained on splitting off the acyl radical.

A second modification of the process according to the invention consists in reacting an anthraquinone compound having in the aryl moiety of 10 preferably of R at least two exchangeable hydrogen atoms, of Formula VIII:

RB (VIII) wherein Q has the meaning given in Formula VIII, to form the corresponding l-sec. alkylaminoor 1 cycloalkylamino-4-aralkylamino-anthraquinone compound and, in any order desired, reacting this with 12 mol of a sulphonating agent and m mol of a compound introducing the radical of Formula VI to form an anthaquinone dyestuff mixture of the average composition of Formula I or II respectively.

W represents, like X in the first process, e.g. the hydroxyl or a low alkoxy group such as the methoxy group or the amino or nitro group, or especially chlorine or bromine.

The starting materials of Formula VIII are known or can be produced by known methods, e.g. by reacting a l-chloroor l-bromoor 1-nitro-4-low-alkoxy-anthraquinone with an aralkylamine of Formula V and, if desired, converting the chlorine or bromine into a low alkoxy group or reducing the nitro group to the amino group.

Starting compounds wherein W is the hydroxyl group can be produced by reacting l,4-dihydroxy-anthraquinone or its leuco compound or a mixture thereof with an aralkylamine of Formula V. They can be used direct without isolation for the condensation with the (sec. alkyl)- amine or cycloalkylamine of Formula IX.

The reaction of the compound of Formula VIII with the (sec. alkyl)-amine or cycloalkylamine of Formula IX to form the corresponding l-sec. alkylaminoor l-cyclo alkylamino-4-aralkylamino-anthraquinone and the con densation of the latter with the compound introducing the radical of Formula VI and the sulphonation to form the end product of Formula I or II are performed analogously to the descriptions given in the first process of this aspect of the invention.

A third modification of the process according to this aspect consists in reacting an anthraquinone compound, containing in the aryl moiety of R4 CH preferably of R at least two exchangeable hydrogen atoms, of Formula X:

0 W H I Y I] O N\ (III-R4 u wherein Y has the meaning given in Formula VII, W has that given in Formula VIII and R and R have the meanings given in Formula V with a (sec. alkyl)-amine or a cycloalkylamine of Formula IX to form the corresponding l-sec. alkylaminoor 1-cycloalkyl-amino-4 (N-aralkyl- N-acylamino)-anthraquinone compound, and, in any order desired, saponifying and reacting this with 11. mol of a sulfonating agent and m mol of a compound introducing the radical of Formula VI to form an anthraquinone dyestulf mixture of the average composition of Formula I or II, respectively.

The starting materials of Formula X are obtained by known methods, e.g. by reacting an anthraquinone compound of Formula VIII with an acylating agent introducing the radical Y, preferably with acetyl chloride or bromide or with a acetoanhydride.

The reaction of the acylamino-anthraquinone compound of Formula X with the (sec. alkyl)-amine or cycloalkylamine of Formula IX and the saponification of the l-sec. alkylaminoor 1-cycl0alkylamino-4-(N-aralkyl-N-acylamino)-anthraquinone compound as well as the sulfonation and reaction with the compound introducing the radical of Formula VI are performed as described in the first process of the invention.

The end products of Formulas I and II are isolated preferably in the form of alkali metal salts, more preferably as sodium salts. They are very soluble in water.

The dyestuffs according to the invention are mixtures of all the isomers falling under their respective formulas, with a few exceptions where such formula represents only individual compounds.

While it is possible to isolate the individual isomers constituting these mixed dyestuffs by known chromatographic techniques, and to identify the position of fiberreactive or non-fiber-reactive Einhom groups and sulfonic acid group or groups in all three aspects, in each isomer, from their magneto-nuclear resonance spectra, such further workup will not lead to products of improved properties, and is, moreover, highly uneconomical, so that it is of no practical value.

The following non-limitative examples illustrate the invention. The temperatures are given therein in degrees centigrade. Where not otherwise stated, parts and percentages are given by weight.

EXAMPLE 1 (I) (a) (l) A mixture of 19 g. of 1-cyclohexylamino-4- bromoanthraquinone, 28.68 g. of 1,5-diphenyl-3-aminopentane, 5 g. of anhydrous potassium acetate, 0.005 g. of cuprous chloride, ml. of n-butanol and 0.10 ml. of water is stirred for 48 hours at a temperature of 100. 30 ml. of methanol are then added to the reaction mixture through a dropping funnel after which the temperature is kept for 30 minutes at 50 whereupon 50 ml. of isopropanol are also added to the reaction mixture. After cooling to room temperature, the precipitated product is filtered off and purified by recrystallization from nbutanol whereupon the compound of the formula:

is obtained.

If instead of 1 cyclohexylamino 4 bromoanthraquinone, equivalent amounts of the 1 cycloalkylamino- 4-halogenoanthraquinones given in the following Table l are used (produced by halogenating the corresponding l-cycloalkylaminoanthraquinones with bromine in glacial acetic acid or with sulphuryl chloride in nitrobenzene), then with otherwise the same procedure, similar end products are obtained.

(II) 54.2 g. of the compound of the formula:

om-om-Q ln-cm-om-Q are added in portions to 13.7 g. of N-methylol chloracetamide until a homogeneous mixture is attained, the mixture is added to 500 g. of 90% sulphuric acid at a temperature of -10 and the solution obtained is stirred for 24 hours at this temperature. The mixture is then poured onto ice, the precipitated condensation product is filtered off, washed neutral with water and dried at 60 in vacuo. It is sulphonated by adding the product to times its amount by weight, of 6% oleum at 23-25 and stirring the mixture for 18 hours. The solution is then poured onto ice, the precipitated dyestuff is filtered off and washed with aqueous 10% sodium chloride solution. The precipitate is slurried in water and the pH of the slurry is adjusted to 7 by the careful addition of dilute sodium hydroxide solution. The dyestuff is then precipitated by the addition of sodium chloride and is filtered off and dried at 60 in vacuo. The dyestufi is obtained as a blue powder which dissolves easily in water with a blue color.

The dyestuflf dyes nylon and wool from a neutral to weakly acid bath in very brilliant blue shades. The dyeing's are very level and have good fastness to light and excellent wet fastness.

O NH- If instead of the l-cyclohexylamino-4-aralkylaminoanthraquinone compound of the above formula, an equivalent amount is used of one of the anthraquinone compounds given above, which is obtained (according to Example 1(a)) by reacting each of the l-cycloalkylaminolhalogeno-anthraquinones listed in Table 1 with 1,5-diphenyl-3-amino-pentane or each of the aralkylamines which are listed in Table 2, and otherwise the procedure given in Example 1(H) is followed, then dyestuffs having a similar good dyeing properties are obtained.

Dyestuffs having similar valuable properties are also obtained if, in each of the examples described above, instead of the 13.7 parts of N-methylol chloracetamide, an equivalent amount of the N-methylol compound of one of the amides given in the following Table 3 is used.

TABLE 3 EXAMPLE 2 (I) (a)(1) A mixture consisting of 19.3 g. of l-(N- acetyl N isopropyl amino) 4 bromoanthraquinone and 26.2 g. of 1,5-diphenyl-3-aminopentane is stirred for 20 hours at a temperature "of The red melt obtained 1 5 is then poured into a mixture of 200 g. of ice and 200 ml. of 2 N HCl whereupon the compound of the formula:

precipitates as a red resin. The aqueous hydrochloride acid phase is decanted and the product of the above formula is dissolved in 100 ml. of 80% sulphuric acid. This solution is stirred for 8 hours at a temperature of 50 and then poured onto ice whereupon the unsulfonated dyestufi of the formula:

A m I CHZ-CHTQ t smashes- TABLE 4 (h) CH3 ca 0 N/ on ll i COGHs Y an (i) CH3 N CHrCHa (i) CHa /CHzCHa 2 O N CHz-CH: l COCH| /CHa /Cg /CHa N 0 1 7 (II) A homogeneous mixture of 50.2 g. of the compound of the formula:

and 13.7 of N-methylol chloracetamide is added to 300 g. of 96% sulfuric acid at 5 and the solution obtained is stirred for 24 hours at this temperature. The temperature is then raised to 23 and 130 g. of 66% oleum are added gradually. The solution is stirred for another 6 hours at 23-25 and then poured onto ice. The product is worked up analogously to the procedure described in Example 1(II).

A dyestuff is obtained which dyes nylon and wool from a neutral to weakly acid bath in very brilliant blue shades. The dyeings are very level, have good fastness to light and, at the same time, excellent wet fastness properties.

If with otherwise the same procedure, instead of the compound of the above formula, an equivalent amount of each of the compounds obtained by condensation of the 1 (N acetyl N sec. alkylamino) 4 halogenoantharquinones listed in Table 4 with 1,5-diphenyl-3- aminopentane or the aralkylamines listed in Table 2 is used, then dyestuifs having similar properties are obtained.

Dyestuffs with similar properties are also obtained if, with the procedure given above, the N-methylol compound of each of the amides (a) to (0:), respectively, given in Table 3 is used instead of N-methylol chloracetamide.

EXAMPLE 3 13.7 g. of a-chloracrylonitrile and 0.1 g. of hydroquinone are dissolved in 65 g. of 93% sulphuric acid at 20, this solution is stirred for 3 hours at a temperature of 3335, cooled to -12", 7.5 g. of oz,oc'-diChlO10dimethyl ether are added dropwise within 1 hour and the mixture is stirred first for 3 hours at 10-12 and then for 4 hours at 13-15.

350 g. of 90% sulphuric acid are then added to this solution after which 50.2 g. of the compound of the formula:

NYE-C are added at a temperature of 5-10". The mixture is stirred for 24 hours at this temperature, then poured onto ice and the condensation product is filtered oif, washed neutral with water and then dried in vacuo at 60. It is sulphonated in 6% oleum for 6 hours at 23-25 as described in Example 1. The dyestuif so obtained dyes nylon and wool from a weakly acid to neutral bath in level, brilliant blue shades; the dyeings have good light fastness and good wet fastness properties, especially good wash fastness.

If instead of the compound of the above formula, an equivalent amount of each of the compounds obtained, respectively, by reacting each of the 4-halogeno-anthraquinones (a) to (q) listed in Tables 1 and 4 with 1,5- diphenyl-3-amino-pentane or each of the phenylalkyl amines (l) to (11), respectively, listed in Table 2 is used with otherwise the same procedure, then dyestuffs having similar valuable properties are obtained.

Dyestuifs having similar properties are also obtained if, with otherwise the same procedure, instead of a-chloroacrylonitrile, an equivalent amount of each of the nitriles, respectively, given in the following Table 5 or the corresponding carboxylic acid amides are used.

In the sulphonation, the hydroxyl groups are sulpliated.

EXAMPLE 4 ,50 g. of the compound of the formula:

CH: O NIH-OE II 1 @v MEG ll time (obtained according to the process of Example 2 by condensation of 1 (N -acetyl N isopropylamino) 4- bromoanthraquinone with 1,5-diphenyl-3-aminopentane and then saponification of the acetyl group) are mixed with 27.5 g. of N-methylol chloracetamide, the mixture is added to 500 g. of sulphuric acid at a temperature of 510 and the whole is stirred for 24 hours. The condensation product is isolated as described in Example 1 and sulphonated in 6% oleum at 25 for 16 hours.

Dyestuffs having similar valuable properties are also obtained if, in Example 4 described above instead of 27.5 g. of N-methylol chloracetamide an equivalent amount of N-methylol u-chloroacrylic acid amide or of N-methylol u,[i-dibromo propionic acid is used.

1 9 EXAMPLE We claim:

1. A dyestuif of the formula:

Q represents one of the radicals wherein:

cyclopentyl or cyclohexyl,

each of R and R represents lower alkyl,

R represents alkylene of from 1 to 2 carbon atoms,

each of Z and Z represents hydrogen, methyl, methoxy,

chlorine or bromine,

each of Z and Z represents hydrogen, methyl or meth- A represents lower alkyl of 1 to 4 carbon atoms or lower alkenyl of 2 to 3 carbon atoms, substituted by from one to two halogen atoms selected from chlorine and bromine p ranges from 1 to 2, and q represents 0 or 1, not more than one SO H group being linked to each of the benzene nuclei in said formula.

2. A dyestufi as defined in claim 1, wherein A represents CCl:CH or -CH Cl.

3. A dyestuif as defined in claim 1, wherein A represents -CHCH Hal l lal wherein Hal represents chlorine or bromine. 4. A dyestuff as defined in claim 2 wherein: Q is /Rl --OH each of R and R being methyl,

R5 is CH CH each of Z Z and Z is hydrogen, Z is chlorine in 4-position, p is l, q is 0, and A is CH Cl.

5. A dyestulf of the formula:

wherein:

Q represents one of the radicals R1 OH cyclopentyl or cyclohexyl,

each of R and R represents lower alkyl,

R represents alkylene of from 1 to 2 carbon atoms,

each of Z and Z represents hydrogen, methyl, methoxy,

chlorine or bromine,

each of Z and Z represents hydrogen, methyl or meth- A represents alkenyl of from 2 to 4 carbon atoms,

p ranges from 1 to 2, and

q represents 0 or 1,

each of R and R being methyl,

R5 is each of Z Z and Z is hydrogen, Z is chlorine in 4-position, p is l, q is 0, and A is CH=CH References Cited UNITED STATES PATENTS 2,426,547 8/1947 Buckley et a1. 260-371 2,475,530 7/1949 Tatum 26037l LORRAINE A. WEINBERGER, Primary Examiner E. J. SKELLY, Assistant Examiner US. Cl. XxR. 8-26, 39, 4Q 

